Margarine and butter compositions



Patented Oct. '25, 1949 Hans W.

. i s; S

Foods, New Jersey No Drawing.

Vahlteich, Edgewater, and Ralph II. Neal, North Bergen, N. 1., tatenIsland, N. Y.,

Inc., New York, N.

and Chester M. Goodassignors to The Best Y., a corporation ApplicationMay 13, 1947,

Serial No. 747,848

12 Claims- (Cl- 99-119) This application is a continuation-in-part ofthe copending applications Serial No. 608,101 filed July 31, 1945,608,102 died July 31, 1945, and 608,380 filed August 1; 1945.

This invention relates to margarine and more particularly to an'improved margarine which possesses marked moisture retentioncharacteristics.

An object of terlal amount of this invention is to retain a mamiikmoisture in margarine'and to prevent the exudation of moisturetherefrom- Another object of this invention is to prevent the so-calledweep of margarine and butoi this invention is simultanesubstantially theexudation of milk moisture from margarine and to retard for relativelyprolonged periods the development of rancidity of margarine and butter.I

Margarine, containing as it does aqueous and oleaginous components,sometimes develops a moisture Tiilm or moisture droplets on the outsidethereof. This leakage of moisture results in underweight prints,increases the danger of bacterial and mold growth and materially affectsthe salability oi the margarine. Then, too, rancidity sometimes developsin margarine which also materially affects the salability of theproduct. Various materials have been heretofore proposed for obtainingthe retention of moisture within the prints of margarine to prevent theweeping of the margarine. Monoglycerides of fatty acids are perhaps themost widely, comter.

Another oblect ously to prevent is satisfactory. Desirably, the alkylgroup oi the I dialkyl'ester of citric acid has at least 12 carbonatoms, and the alkylene group of the dialkylene ester of citric acid hasat least 16 carbon atoms.

The preferred concentration of the dialkyl ester is .2 to .5% by weightof the ester in the margarlne when the alkyl groups in the ester havefrom 8 to 16 carbon atoms and .1 to .3% by weight of the ester when thealkyl group has at least 16 carbon atoms. The preferred concentration ofthe dialkylene ester of citric acid is V to by weight of the ester inthe margarine, and desirably the alkylene group of the dialkylene esterhas at least idca'rbon atoms. Monoalkyl esters of citric acid,especially monesters in which the alkyl group has at least 16 carbonatoms also manifest marked moisture retention characteristics whenincorporated in margarine. However, a greater quantity of suchmonoesters is required than diesters to eflectsimilar moisture retentionproperties, and a. greater concentration of such monoesters in margarineis sometimes objectional from a flavor standpoint.

While the dialkyl ester of citric acid and the dialkylene ester ofcitric acid sometimes appear mercially used preparations for thispurpose.

But monoglycerides of fatty acids have substantially no effect onretarding the rancidity of margarine. v v

In accordance with this invention, a new margarine is produced which hashigh moisture retaining properties and which does not manifest ieakageor weeping. In addition, in accordance with another aspect of thisinvention, the rancidity of margarine is materially retarded. The newmargarine comprises in addition to the components, such as 'deodorizedfats, milk, salt, lecithin, vitamins, etc., a dialkyl or dialkyleneester of citric acid in which the alkyl or alkylene group has at least 8carbon atoms. The concentration of the dialkyl or dialkylene esters ofcitric acid in the new margarine may vary over to improve to a smalldegree the retardation of rancidity in margarine, the new margarine maybe markedly improved from a rancidit standpoint by the addition theretoof a monoalkyl or monoalkylene ester of citric acid. The monoalkyl ormonalkylene ester of citric acid which may also be included in the newmargarine, may have any number of carbon atoms in the alkyl or alkylenegroup, although conveniently it contains the same number of carbon atomsas the dialkyl or dialkylene ester which is included in usual widelimits depending upon inter alia, the,

the composition. For example, the monoalkyl or monoalkylen esters mayhave at least 8 carbon atoms in the alkyl or alkylene group, or themonoalkylene ester may have at least 16 carbon atoms in the alkylenegroup, 'or the monoalkyl ester may have at least 12 carbon atoms in thealkyl group. By employing both the dialkyl or dialkylene esters ofcitric acid and the monoalkyl or monoalkylene esters of citric acid, theresulting new margarinehas high moisture retaining properties, and inaddition, manifests a marked resistance to rancidity. The amount ofmonoalkyl or monalkylene esters of citric acid may be within the rangeof 002 to 1%, and preferably within the range of .01 to .1%, by weightin the margarine. Conveniently, the diesters and monoesters of citricacid may be prepared simultaneously. This simultaneous pro duction ofthe mono and corresponding diesters of citric acid can be achieved byreacting the required amount of anhydrous citric acid or citric acidmonohydrate with an alkyl or alkylene .alcohol to produce the desiredamount 01' the diot citric acid, may be a single specie or a pluralityoi species. For example, it is advantageous in some cases to incorporatein the margarine, a mixture of distearyl and dipalmityl citratestogether with monostearyl and monopalmityl citrates, while in othercases, the addition 'ofa mixture of distearyl citrate and monostearylcitrate is desirable. If a mixed alcohol is employed for the preparationof the citric acid esters, the resulting mixture contains some-mixed toof palmityl and stearyl alcohols'is reacted with' citric acid in therequired proportions, the resulting product comprises in addition todipalmityl rs ether Wi h an amount of the cori'e- 5 citrate, distearylcitrate, monopalmityl citrate sponding monoesters of citric acid.- andm'onostearyl citrate, some mixed diesters of The diester of citric acidmay be incorp citric acid and paimityl and stearyl alcohols. i e a a iat y age of its preparati The eflicacy oi. the dialkyl and dialkyleneesters or in the deodc'rize'd fat prior to'the use'oi! the fat of itr idin in reasing substantially the mois-v in the production ofthe-margarine; To prevent l0. ture retention characteristics ofmargarine is the exud on of milk moisture from. nd retard demonstratedin the following tables in which the r noi y th margarine, a mixture ofdimargarines containing a mono or a dialkyl ester alkyl and monoalkylesters of citric acid or a bi citric acid ora mono or a dialkylene esteror mixtur of dia ylen and monoalkyiene esters citricacidiarecompared witmargarine re ared v of citric acid is used. Preferably, suchmixture- 15under identical *conditions but without these. is added to the fatshortly 'after'the deodorizacompounds For further. comparison, margarinetionof the fat, since the rat starts togdeteriorate ccntalnin g' mst mtincluded m this immediately upon the completion of the -de0dOrtesting,Iii-Table 1,- a margarine containing a ization. The diesters of citricacid or the mix mixture of, mohostearylcitrate,'distearyl'citrate tureof the mono and diesters of citric' acid may andjtristearyl citrate, orcontaining'pure mono,- be incorporated at other points in the-process,stearyl citrate, or .containing pure distearyl such as in the churningstep, depending upon the citrate; or' containing pure -tristearylcitrate particular sequence of processing steps employed. is. compared.with, samples of margarine, des- 'However, it is desirable that themonoester and v ignated" in the table as the control samples, diester ofcitric acid be'added subsequent to the 5 which were preparedunderidentical conditions deodorization of the fat, since av majorportion except, that no ester-o1 citric acid was incorpoj; of the estersof citric acid may be renderedinrated therein. In Table-2, margarinewithout eii'ective in the deodorization step. any citric acid esters iscompared with margarine .The dialkyl or dialkylene esters of citricacid, containingp'ure monostearyl citrate or pure didesirably withmonoalkyl or monoalkylene esters 3o stearyl citrate or'a mixture ofmono, diand trifstearyl citrates. Table 3 shows a comparative testing ofa margarine having incorporated therein a mixture oi mono, di and.trioctyl citrates, a

margarin having incorporated therein a, mix- ,tureoi' mono, di andtrilauryl 'citrates, a margarine having incorporated therein a mixtureof' mono,'di and trioleyl citratesand a margarine designated in thetable as the control, which was prepared under identical conditions,except that no esters of citric'acid were incorporated therein.

Table 1 Petr-cent i nois- Fr t are a or ee mo s ure Percent mois-Observation oi e g fi t f ff 3332 Sample moisture leakage alter blending0 addition of 1 on rolls in mixer prior $3 3 23? excess water 7 toaddition in mm 8 and blending of extcelss in mixer Cubic centimden 1.Control (Margarine without addition of any ester) Serious leakage-..15.5 14.8 15 2. Margarine containing 0.25% MonostearylCitrate Slightleakage 15. 5 1 l9. 0 3. 3. .Margarine containing 0.25 DistearylCitrate-pure No leakage. l5. 7 v 18.4 1. 4. Margarine containing 0.25Tristearyl Citrate pure Serious leakage..- 13. 5' 12. 2 ii) 5. Margarinecontaining 0.25 o ofa mixture comprising about 50% Di- Noleakage. 16.619.0 1. stearyl Citrates anc 15% Monostearyl Citrates. I 6. Margarinecontain ing 0.5 Monostearyi Citrate do 15. 8 18. 7 2. 7. Margarinecontainmg 0.5 Distearyl Citrate -.do 15.4. 18.8 1. 8. Margarinecontainmg 0.5% Tristearyl Citrate Serious leakage 13. 8 12.3 '19 0.Margarine containing 0.5% oi a mixture comprising about 50%Di- Noleakage 15.,0 18.1 l. stearyl Citrate and about 15% Monostearyl Citrate.I a 10. Control (Margarine without addition of any ester) Seriousleakage.... 15. 2 14. 6 18 Table v2 7 Percent fmois- Fr s awn?Percentmols' ro a i iri ng ih Observation of 00 F. and mixer afterSample moisture leakage sitar blending 0 addition oi on rollsintomaifigiit ligior 33 3 333; exacts? wgtlgr n 1 an on g oi extcessmker in mixer wa er I 1 Cubic centimeters 1. Margarine without additionof any ester Serious leakage.-. 14. 2 14. 0 16. 5 2. Margarinecontaining 0.25 Monostearyl Citrate pure Slight leakage..." '15. 5 18. 13. 5 r l' no containing 0.25 o Distearyl Citrate-pure No leakage 15.417. 7 1. l 4- Margarine containing 0.257 of a mixture comprising about50% .do 15. 2 18- l l a d gi ih tiii i $15 5? ii I i in bo 507 d i 11 1s a 'con g o a m ture com rs a lit o 5.3 .5 Distsaryl Citrate and about15% of Monostearyl itrat I a Table 3 Percent moistc hgzr i ng at Percentmois $385355? Observation of F. and g a gg g mixer alter Sample moistureleakage aitcr blending addition of on rolls in mixer rior excess excesswater to addition and blendmg and blending of excess in mixer mixerwater Cubic centimeter: 1. Control (margarine without addition of anyester) Serious ieakage 13. o 13. 6 15 2. Margarine containing 0.25% of amixture comprising about 50% of!) No leakage 15. 0 14. 9 l3 dioctylcitrate and about 15% of mono'octyl citrate. 3. Margarinecontaining0.25% 0! a mixture comprising about 50% do 15. 2 16. Y 8

dilauryl citrate and about of monolauryl citrate. 4. Margarinecontaining 0.25% of a mixture comprising about 50% of Slight leakage...15.0 15. 1 l4 dioleyl citrate and about 15% of mono-oleyl citrate. 5.Margarine containing 0.25% of a mixture comprising about 60% 111- Noleakage 15. 4 18.1 0.5

stearyl citrate and about 15% monostearyl citrate. 8. Control (margarinewithout addition of any ester) Serious leakage 14. 5 13. 7 15 7.Margarine containing 0.50% of a mixture comprising about 50% di, Noleakage 15. 1 17.7 4

octyl citrate and about 15% of monooctyl citrate. 8. Margarinecontaining 0.50% of a mixture comprising about 50% dido 15.1 17. 5 4

lauryl citrate and about 15% monolauryl citrate. 9. Margarine containing0.50% of a mixture comprising about 50% of do 15.6 16. 9

dioleyl citrate and about 15% of monooleyl citrate. 10. Margarinecontaining 0.507 of a mixture comprising about 50% do 15.0 17.9 0-5distearyl citrate and about 15% monostearyl citrate.

In the tables, the observation of the moisture leakage on the rolls isan index of the ability of the margarine in the form of a print toretain moisture. Again the amount of free moisture remaining in themixer after addition of the excess moisture is inversely correlated withthe ability of the margarine in the form of a print to retain moisture(ie. the more moisture remaining in the mixer, the less ability themargarine has to retain excess moisture).

The samples of margarine for the determination of the relative moistureretaining efllcacy were prepared as follows:

A margarine emulsion was prepared by mixing 80 parts of deodorized,hydrogenated vegetable margarine oils containing about 45% of soya beanoil and about 55% cottonseed oil, about 17 parts of cultured skim milkcontaining about 0.5% sodium benzoate, and 3 parts of table salt. Thedeodorized, hydrogenated oil employed contained vitamins and 0.10% ofvegetable lecithin. Also, in the case of the samples noted in the tableas containing esters of citric acid, the esters were added to themargarine oil prior to the production of the emulsion. The emulsion waspermitted'to solidify by passing it over a chilled steel roll. It

' was then tempered by allowing it to stand at room temperature forabout 16 hours, after which it was formed into prints. 400 grams of thetempered margarine were placed in a hand mixer; the margarine waspartially plasticized by making 10 revolutions of the mixing handle. 50grams of the margarine thus mixed were removed for determination ofmoisture content. To the 350 grams of margarine remaining in the mixer,18 ccof water were added, and the product containing the added water wasmixed by making 50 revolutions of the mixing handle, The free moistureremaining in the mixer and not incorporated in the margarine wasmeasured by volume; also, the moisture content of the margarine itself,to which the excess water had been added, was determined after drainingof! the free water which had not been incorporated into the margarine.

Thus, the moisture retaining capacities of these various preparationswere evaluated in four ways:

1. By visual observation (product dry or showing moisture leakage),while coming over the chill roll and during printing after tempering.

This bears on wet wrappers encountered in margarine production in casesof moisture leakage,

and, in addition, is one way of estimating the relative tightness withwhich the milk moisture is bound in the finished margarine emulsion.

2. By the actual quantitative determination of the moisture content ofthe finished prints.

3. By visual observation and volume measurement of free water notincorporated into the margarine by the standardized mixing proceduredescribed, after the addition of excess water to the finished print.

4. By the quantitative moisture content of the product to which excesswater had been added after tempering the finished prints. I

A review of Tables 1 and 2 reveals that no leakage was manifest by themargarine on the rolls when the margarine contained 0.25% or 0.5% ofdistearyl citrate. Also, no leakage was observed when 0.15% of a.mixture of distearyl citrate, monostearyl citrate and tristearyl citrate(i. e. 075% of distearyl citrate) was used. Onthe other hand, slightleakage occurred when 0.25% of monostearyl citrate was incorporated inthe margarine, and serious leakage also occurred when 0.25% or 0.5% oftristearyl citrate was employed. In fact, substantially the same seriousleakage was discernible in the samples of margarine in which tristearylcitrate was used as when no ester was incorporated in the composition.At higher levels such as 0.5%,. the monostearyl citrate showedsatisfactory moisture retaining characteristics.

In Table 3, serious leakage was observed in the control sample ofmargarine having no esters incorporated therein, but no leakage wasdiscernible when there was used 0.25% of am-ixture comprising aboutdioctyl citrate and about 15% of monooctyl citrate, or 0.25% about'50%dilauryl citrate and about 15% of monolauryl citrate, or 0.25% of amixture comprising about 50% distearyl citrate and about 15% monostearylcitrate. Accordingly, these data demonstrate that a relatively smallquantity of a dialkyl ester increases materially the moistureretentioncharacteristics of margarine. Likewise, the dialkyiene citratesalso markedly improve the moisture retention characteristics ofmargarine as illustrated by the use of 0.5% of a mixture of about 50%dioleyl citrate and about 15% of monooleyl citrate as shown in Table 3.And as shown in the copending applications of applicants, Serial Numbers608,101, 608,102 and determination or the of a mixture of -7 .380. thepresence of a small quantity ofv monoalkyl or monoa'llgvlene esters ofcitric acid markedly retard the rancidity of compositions containingglyceridic oils, including the fats in margarine. Therefore, byincorporating both a dialkyl or dialkylene citrate having at least 8carbon atoms in the alkyl or alkylene group, and a monoalkyl ormonoalkylene citrate in the maracid and the alcohol in proportions whichfavor the formation of the di and monoesters in. the ratio desired inthe mixture. The esteriflcation may be conducted by any of the wellknown methods employed for the production of esters,

and the resulting reaction mixture which may comprise not only the monoand diesters of citric acid, but a quantity of thetriesters of citricacid, is subjected to treatment by fractional crystallization orselective extraction with a suitable solvent, if desired, which removesthe major portion of the triesters of citric acid present. If desired,the mixture comprising principally the diester with a lesser amount ofthe mono and some of the triester, may be used in the margarine. Toproduce-the mixture, 8. monohydric primary or secondary alkyl oralkylene alcohol,':tor example, may be reacted with citric acidmonohydrate, by heating to an elevated temperature, such as 150 C.,under reduced pressure until the reaction is complete. The reactionproduct without further' purification may be incorporated in themargarine by addition during any stage of the production of themargarine. The term "margarine in the description and claims includesbutter, such as cow's butter.

Examples of the mono and di citric acid esters which may be incorporatedin the margarine are the citric acid esters ,of the following alcohols:2

ethyl-hexanol, octanols, decanols, dodecanols, hexadecanols,octadecanols, cosanols, docosanols, 2-ethyl hexenols, octenols,decenols, dodecenols, hexadenols, octadenols, cosenols and docosenols.

A more comprehensive understanding of the invention is obtained byreference to the following examples.

Example 1.'Margarine containing monostearyl citrate, 'disteariil citrateandtristearyl citrate Monostearyl citrate and distearyl citrate may beincorporated in margarine by dissolving a mixture of monostearylcitrate, distearyl citrate and tristearyl citrate in a small quantity ofthe hydrogenated and deodorized oil employed for the margarine, andadding that solution of the stearyl esters to the body of thehydrogenated and deodorized margarine oil. For example, 2.5 lbs. of .amixture of monostearyl citrate, distearyl citrate and tristearylcitrate, prepared as described herein, are added at 145 F. to about 2lbs. of a hydrogenated and deodorized margarine 011 comprising about75%v cottonseed oil and about 25% soya bean oil. This solution of themixture of stearyl citrates is added at a temperature 01 about 110 F. toabout 800 lbs. of hydrogenated and deodorized margarine oil comprisingabout 75% cottonseed oil and about .of soya bean oil, and includingabout 2 lbs. of lecithin and aminor quantity of the other usualconstituents of margarineoil, such as vitamins. The

stearyl' citrates are thereby substantially uni-' formly dispersedthroughout the margarine oil.

This body 01' margarine 011 containing the stearyl citrates isthoroughly mixed or churned with about 170 lbs. of cultured milk inaccordance with the customary practice of margarine manufacture. Duringthe mixing or churning, and preferably toward the end of the churning.about lbs. of salt are added. The resulting mixture is then chilled byany suitable means, such as passage over chilled steel rolls or throughice' water, or through an internal chilling unit. The chilled. emulsionis kneaded into a mass, formed 'into prints and packaged. v

v The mixture of monostearyl citrate, distearyl v citrate and tristearylcitrate for this purpose is prepared as follows: I

12.1 kilos of citric acid monohydrate are added to 30 kilos ofcommercial s'tearyl. alcohol (containing some palmityl alcohol) which ispre-.

viously melted. During the addition, the mixture is agitated- Themixture is held at C. under reduced pressure for a period of 1% hours.At the end of this period, boiling and foaming ceases substantially. Theresulting product which consists of a mixture of about 10 to 15%monostearyl citrate, about 50% distearyl citrate and 1 the remaindertristearyl citrate together with a quantity oi mono, di and tripalmitylcitrates has an acid value of about'83, a saponification value of about249 and a melting point of about 51 to 68 C. and a color on the Lovibondscale of about 35Y-5.8R.

- About 800 lbs. of hydrogenated and deodorized margarine 011 comprising-"about 75% cottonseed -oil and about 25% soya bean oil and includingabout 2 lbs'. of lecithin and a minor quantity of the other usualconstituents of margarine oil such as vitamins, are thoroughly mixed orchurned with about lbs. of cultured milk. During the mixing or churning,and preferably toward the end of the churning, about 35 lbs. of salt areadded. The resulting mixture is then chilled through a chill vat. Inthis method of chilling, the churned mixture of oiland milk is sprayedinto a vat oi ice water. product is collected and worked mechanically orkneaded to remove entrapped ice water. This working may be performed ona large round revolving table with a corrugated wooden kneading roll.During the working. a water paste pre-' pared by thoroughly mixing about2 lbs. of water and 1 lb. 01 a mixture of monolauryl citrate, dilaurylcitrate and trilauryl citrate produced as described herein, isthoroughly incorporated in the mass of chilled churned margarine. The'worked mass is then formed into prints and packaged.

A mixture of monolauryl citrate, dilauryl citrate and trilauryl citrateis prepared in a similar manner to that described in Example 1 for thepreparation of the mixed monostearyl citrate, distearyl citrate andtristearyl citrate except that 250 lbs. of commercial lauryl alcohol isused instead of the 30 kilos of commercial stearyl alco- The chilled.

hol, and 120 lbs. oi anhydrous citric acid is used trample 3.Maraarinecontaining distearul citrate I About 3 lbs. oi distearyl citrate aredissolved at about 145 F. in about 3 lbs. oi a hydrogenated anddeodorized vegetable oil to be utilized as the oil-component in themargarine. This solution oi distearyl citrate is added at a temperatureoi about 110 F. to about 800 lbs. oi hydrogenated and deodorizedmargarine oil comprising about the mixture oi about to Example 5 .-,'-Maraarine containing monooleill cit- 'l5% cottonseed oil, about 15% soyabean oil and about 10% peanut oil, and including 2 lbs. oi lecithin anda minor quantity oi the other usual constituents oi margarine oil suchas vitamins. The body oi margarine 011 containing the distearyl citrateis thoroughly mixed or churned with about 170 lbs. oi cultured milk.During. the mixing or churningabout 30 lbs. of salt are added. Theresulting mixture is then chilled, kneaded, iormed into prints andpackaged.

The substantially pure distearyl citrate employed in this example isproduced by initially preparing a mixture oi monostearyl citrate,distearyl citrate and tristearyl citrate as described in Example 1, andthe distearyl citrate is separated irom the resulting reaction mixtureby iractional crystallisation irom a suitable solvent, such as ethanolor isopropanol, the tristearyl citrate coming out oi solution before thedistearyl citrate. The monostearyl citrate is retained in solution.

trioctyi citrates was separated in deodoriled ior about 1% hours underreduced pressure at 150 C. The odorless and light-colored and limpidproduct was iound to have an acid value oi 147.6 and a saponiilcationvalue oi 435 compared with theoretical values ior dioctyl citrate or 135.and 405 respectively. The mixture contained about 20%. monooctylcitrate, about 50% dioctyi citrate and the remainder trioctyl citrate.

rate, dioleyl citrate, triolevl citrate, monostearll citrate, distearuicitrate and tristearill citrate Ab0ut"7.5 lbs. of a mixture prepared asdescribed herein oi monooleyl citrate, dioleyl citrate, trioleylcitrate, monostearyl citrate, distearyl citrate and tristearyl citrateare added to about 7.5 lbs. of an oil to be utilized as the oilcomponent of the margarine;- The mixture oi oieyl and stearyl citratesis added at a temperature oi about 110 F. to about 800 lbs. oi amargarine oil comprising about 'l5% cottonseed oil, about 15% soya beanoil and about 10% peanut oil. The margarine is then mixed or churnedwith about 170 lbs. oi "cultured milk, and about lbs, oi salt are addedduring the churning. The mixture is then chilled, kneaded, formed intoprints and packaged. I

The mixture to be incorporated in margarine oi the distearyl citrate,thedioleyl citrate and the corresponding mono and triesters together withthe mixed esters is prepared as follows:

A mixture of 14 kilos of commercial oleyl alcohol and l4'kilos ofcommercial stearyl alcohol are melted. To this mixture is added 10.2kilos of anhydrous citric acid. During the addition,

the mixture is agitated. The mixture is heated and held for a period of1% hours at 150 C.

under reduced pressure. At the end oi this period, boiling and foamingceases substantially.

The mixturecontains the distearyl citrate, di-

' oleyl citrate and their corresponding mono and Example 4.-liaraarinecontaining monooctyl citrate, dioctul citrate and trtoctul citrate About8' lbs. of a mixture of monooctyl citrate,

I dioctyl citrate and trioctyl citrate prepared as described herein areadded at a temperature oi about 110 F. to about -800 lbs. of a margarineoil comprising about 75% cottonseed oil, about 15% soya bean oil andabout 10% peanutoil. This addition of the mixture of octyl citrates maybe made in the storage tank, if desired, at any time prior to thepumping of the margarine oil to the churn or mixer. The margarine oilwith the mixture oi octyl citrates substantially dispersed throughoutthe mass oi the oil is then mixed or churned with milk. During thechurning, about 30 lbs. of salt are added. The resulting mixture is thenchilled,"

kneaded, formed into prints and packaged.

A mixture or monooctyl citrate, dioctyl citrate and trioctyi citrate isprepared as iollows:

150 lbs. of octyl alcohol (commercial 2-ethyl hexanol) were heated in aclosed vessel with 137 lbs. of anhydrous citric acid ior 6% hours at150-155 C. The reaction product comprised three layers, an upper esterlayer. a middle aqueous layer and an almost crystalline sludge. Theupper oily layer which comprised mono, ,di and about 170 lbs. ofcultured triesterstogether with mixed esters containing both stearyl andoleyl groups.

Example 6.Dairu butter containing mum or ,dtalkul ene citric acid estersand monoalkzli or monoalkylene citric acid esters Dialkyl or dialkylenecitric acid esters and monoalkyl or monoalkylene citric acid esters maybe incorporated in dairy butterin the same manner that these esters ,ormixtures oi esters are incorporated in margarine. For example, theesters may be added to butter oil instead oi margarine oil as describedin Examples 1, 3, 4 and 5, or the mixture of mono and diesters may beincorporated in the butter by use oi a paste containing the esters asdescribed in Example 2. Ifjthe esters are added to the butter oil, thebutter oil may be prepared, for example, as described in U- S. Patent2,414,837 granted to the assignee ofiL. K. Riggs on January 28. 1947.After relatively uniform dispersion or the esters throughout such butteroil, the butter oil may be formed into butter as described in said U. 8.Patent 2,414,837. In the event a water paste of the citric acid estersis employed, the paste may be worked into the dairy butter in the samemanner as it is worked into margarine as described in Example 2. Thesame quantities oi mono and diesters oi citric acid may be utilized asemployed for margarine in Examples 1 to 5.

11 in margarine, or butter in accordance with this invention markedlyimproves the flavor life and prevents the so -called flavor reversionwhich is characteristic of certain glyceridic oils such as" soya beanoil. Thi improvement-in flavor'life is shown in the following table inwhich a, sample of butter fat containing .0 by weight of puremonostearyl citrate was compared periodically over a period of 38 dayswith an identical sample 'therein- 0.1 to 0.3% by weight of a. dialkylester of;

.3. A margarine containing oleaginous and aqueous components and havingincorporated citric acid in which the alkyl group has at least 16 carbonatoms. 1

4. A margarine containing oleaginous and aqueous components and havingincorporated therein 0.2 to 0.5% by weight of a dialkyl ester of citricacid in which the alkyl group has from of butter fatwithout any ester orother compo- 8 to 16 carbo'n' atoms.

. sition added'to it. 6.- A margarine containing oleaginous and FlavorFresh Days 12 Days 18 Days 26 Days 38 Days Butter fat containing .05% byGood-Sweet Good-Sweet Good-swcet Good-Sweet Good-Sweet Good-Sweet\viiigltit of pure uionosteuryl Cream Flavor. Cream Flavor. CreamFlavor. eam Flavor. Cream Flavor. Cream Flavor. en ru e.

'Sanio butter fat without any ..do -d0 Fair-old butter Fair-old butterPoor-strongfla- Pooh-strong flaestcr therein flavor. flavor. vor. vor.

The butter fat containing the pure monostearyl citrate and that withoutany ester therein. weresubjected to storage under identical conditionsat 90 F.

In order to avoid uncontrolled variables, the butter fat for thistesting was prepared from 2 quarts of fresh heavy cream. The-fat wasobtained from-the cream by first churning it into butter, melting theresulting butter'at 42 C., decanting the fat and filtering the decantedfat after centrifuging. The tests were made onthis butter fat. Thebutter fat was divided into two portions and to one portion .05% byweight ofpure monostearyl citrate was added. The flavor testing wasdetermined by four experts skilled in discerning the flavor of foodproducts, and all four experts were in agreement with the flavorcharacteristics recorded inthe table. This improvement of the-flavorlife resulting from the incorporation of monoesters in margarine isparticularly important with butter fats and other glyceridic oils suchas soya bean oil which are susceptible to detrimental changes in flavorover a period of time.

The terms and expressions which we have employed are used as terms ofdescription and not of limitation, and we have no intention, in the useof such terms and expressions, of excluding any equivalents of thefeatures shown and described or p'ortions thereof, but recognize thatvarious modifications are possible within the scope of the inventionclaimed. 1

What is claimed is:

1. Av composition of matter containing oleaginous and aqueous componentsand selected from the class consisting of margarine and dairy butter,and having incorporated therein 0.05 to 1.5% by weight of a diester ofcitric acid selected from the class consisting of dialkyl esters ofcitric acid and dialkylene esters of citric acid, in which theaIkylandaIkyIene groups have at least 8 carbon atoms. 1

2. A composition of matter containing oleagi.-'

nous andaqtieous components and selected from the classconsisting' ofmargarine and dairy butter, and having incorporated therein 0.05 to 1.5%by weight ,o fIa die's'ter'of citric acid and 0.002 to 1% of a 'rn'ester of citric acid, said diester or citric acidbem'g selected from theclass consisting of dialkyl esters of citric acid and dialkyl-.

ene esters of citric acid, in which the alkyl and alkylene'groups haveat least 8 carbon atoms and said monoester of citric acid being'selectedfrom the class consisting of monoalkyl esters of citric I acid andmonoaikylene esters ofcitric acid.

aqueous components and having' incorporated therein to /2% by weight ofa dialkylene ester of citric acid in which the alkylene group has atleast 16 carbon atoms.

6. A margarine containing oleaginous and aqueous components and havingincorporated therein 0.1 to 0.3% by weight of a dialkyl ester of citricacid in which the alkyl group has at least 16 carbon atoms and 0.01 to0.1% by weight of a monoalkyl ester ,of citric acid in which the alkylgroup has at least 16 carbon atoms.

7. A margarine containing oleaginous and aqueous components and .havingincorporated therein 0.2 to 0.5% by weight of a dialkyl ester of citricacid in which the alkyl group has from 8 to 16 carbon atoms and 0.01 to0.1% by weight of a monoalkyl ester of citric acid in which the alkylgroup has from 8 to 16 carbon atoms.

8. A margarine containing oleaginous and aqueous components and havingincorporated therein A to by weight of a dialkylene ester of citric acidin which the alkylene group has at least 16 carbon atoms and 0.01 to0.1% by weight of a monoalkylene ester of citric acid in which thealkylene group has at least 16 carbon atoms.

9. A margarine containing oleaginous and aqueous components and havingincorporated therein 0.1 to 0.3% by weight of distearyl citrate.

10. A margarine containing oleaginous and aqueous components and havingincorporated therein 0.1 to 0.3% by weight of a mixture of distearylcitrate and dipalmityl citrate.

11. A method of improving a composition of matter containing oleaginousand aqueous components and selected from the class consisting ofmargarine and dairy butter, said method comprising incorporatin in thecomposition of mat ter 0.05 to 1.5% by weight of a diester of citricacid selected from the class consisting of dialkyl esters of citric acidand dialkylene esters of citric acid, in which the'alkyl and alkylenegroups have at least 8 carbon atoms.

12. The method of producing a composition of matter containingoleaginous and aqueous components and selected from the class consistingof margarine and dairy butter, said method comprising incorporating inthe composition of mat- 7 ter 0.05 to 1.5% by weight of a diester ofcitric atoms, and said monoester of citric acid being selected from theclass consisting of monoalkyl esters of citric acid and monoalkyleneesters of UNITED STATES PATENTS citric acid. v

- Number Name Date Y g -g mm 1,857,274 Emhardt May 10. 1932 CHESTER" MGOODING 2,122,716 Graves July 5, 1938 6 2,197,269 Guillaudeu Apr. 16,1940 REFERENCES CITED The following references are of record in the fileof this patent:

